Catalyst compositions having enhanced acidity for bi-reforming processes

ABSTRACT

Methods for bi-reforming over a modified red mud catalyst composition, one method including providing a methane feed in the presence of carbon dioxide and steam to react over the modified red mud catalyst composition at increased temperature and increased pressure to produce synthesis gas comprising H2 and CO, the composition comprising red mud material produced from an alumina extraction process from bauxite ore; nickel oxide, the nickel oxide present at between about 5 wt. % to about 40 wt. % of the modified red mud catalyst composition; and a Periodic Table Group VIB metal oxide, the Group VIB metal oxide present at between about 1 wt. % and about 30 wt. % of the modified red mud catalyst composition.

BACKGROUND Field

Embodiments of the disclosure relate to catalyst compositions for use in reforming processes. In particular, certain embodiments of the disclosure relate to Periodic Table Group VIB metal oxide containing catalyst compositions for and methods of bi-reforming.

Description of the Related Art

Bi-reforming is a green method for the production of synthesis gas (syngas, H₂ and CO), since it utilizes the two greenhouse gases of CH₄ and CO₂ as reactants. In addition, it can offer certain advantages over dry reforming and steam reforming with respect to catalyst deactivation and final product ratio. The general chemical equation representing bi-reforming is shown below.

3CH₄+CO₂+2H₂O

8H₂+4CO  Eq. 1

Bi-reforming technology combines dry reforming and steam reforming of methane to produce syngas. Unlike dry reforming, bi-reforming produces a syngas that is both flexible (with variability in the CO₂/H₂O ratio) and meets the 2/1 H₂/CO ratio required by many higher-value products, for example, higher oxygenates. In addition, the presence of steam provides a higher oxidant level in bi-reforming that addresses the inevitable and typically intolerable carbon deposition in dry reforming.

However, one of the main challenges of bi-reforming is to develop catalysts that are resistant to high temperatures and the presence of a more oxidative environment due to steam. Suitable catalysts for bi-reforming should be resistant to high temperatures and the presence of a more oxidative environment due to steam addition. Methane reforming can quickly deactivate catalysts due to coke formation on the surface of catalysts. In addition, high temperatures for methane conversion can lead to catalyst deactivation by coking or sintering. Nickel catalyst with aluminum oxide and magnesium oxide as supports is used for methane reforming.

However, present catalyst technology is insufficient in some processes to provide cost-effective and durable means for bi-reforming.

SUMMARY

Applicant has recognized a need for compositions of Periodic Table Group VIB (Group VIB) metal oxide containing red mud to be applied in systems and processes for bi-reforming. Enhanced-acidity Group VIB catalyst compositions are disclosed, in some embodiments further including nickel. The enhanced-acidity Group VIB catalysts also contain in some embodiments Fe, Al, Si, Na, Ca, and Ti oxides from red mud. In embodiments of the present disclosure, red mud acts as a catalyst in addition to or alternative to a catalyst carrier. Disclosed compositions are useful as a catalyst in bi-reforming processes for the conversion of methane to syngas, according to Equation 1. Utilization of red mud in bi-reforming processes provides the concurrent advantages of utilizing a waste material (red mud) and producing useful H₂, while also using two greenhouse gases (CO₂ and CH₄) as reactants.

Red mud is a caustic waste material produced from bauxite ore processing for alumina extraction, and is utilized here as a catalyst for bi-reforming processes. Surprisingly and unexpectedly, without being specifically designed as a catalyst (for example using specific zeolitic structure), red mud waste material can be readily modified for use as a catalyst. Red mud generally includes a mixture of transition metals such as Ti, Fe, and Al, which make it an advantageous catalyst for bi-reforming processes, for example once modified with nickel and molybdenum.

Embodiments disclosed here apply red mud as an active catalyst support, promotor, in addition to or alternative to catalyst to produce hydrogen through bi-reforming of methane, optionally followed by a water-gas shift reaction to produce additional H₂.

Therefore, disclosed here are methods for bi-reforming over a modified red mud catalyst composition, one method including providing a methane feed in the presence of carbon dioxide and steam to react over the modified red mud catalyst composition at increased temperature and increased pressure to produce synthesis gas comprising H₂ and CO, the composition comprising: red mud material produced from an alumina extraction process from bauxite ore; nickel oxide, the nickel oxide present at between about 5 wt. % to about 40 wt. % of the modified red mud catalyst composition; and a Periodic Table Group VIB metal oxide, the Group VIB metal oxide present at between about 1 wt. % and about 30 wt. % of the modified red mud catalyst composition.

In some embodiments, the Group VIB metal oxide comprises at least one metal selected from the group consisting of: chromium, molybdenum, and tungsten. Still in other embodiments, the increased temperature is between about 500° C. to about 1000° C. In some embodiments, the increased temperature is between about 600° C. to about 800° C. In other embodiments, the increased temperature is about 750° C. In certain embodiments, the increased pressure is between about 5 bar and about 20 bar. In other embodiments, the increased pressure is between about 10 bar and about 15 bar. Still in other embodiments, the increased pressure is about 14 bar.

In some embodiments, gas hourly space velocity of the methane feed, carbon dioxide feed, and steam feed mixed is between about 1000 h⁻¹ to 10000 h⁻¹. Still in other embodiments, the composition includes at least one component selected from the group consisting of: Fe₂O₃, Al₂O₃, SiO₂, Na₂O, CaO, and TiO₂. In certain embodiments, a majority of the particles of the composition have a particle size of less than about 70 μm. And in other embodiments, the nickel oxide is present at between about 10 wt. % to about 30 wt. % of the modified red mud catalyst composition.

Still in other embodiments, the nickel oxide is present at between about 15 wt. % to about 25 wt. % of the modified red mud catalyst composition. In certain embodiments, the nickel oxide is present at about 23 wt. % of the modified red mud catalyst composition. In some embodiments, the Group VIB metal oxide is present at between about 1 wt. % to about 20 wt. % of the modified red mud catalyst composition. Still in other embodiments, the Group VIB metal oxide is present at between about 1 wt. % to about 10 wt. % of the modified red mud catalyst composition. In certain embodiments, the Group VIB metal oxide is present at about 5 wt. % of the modified red mud catalyst composition.

In some embodiments, conversion percentage of methane reaches up to about 35%. In other embodiments, a molar ratio of methane:carbon dioxide:steam is about 3:1:2. Still in other embodiments, produced H₂ is at least about 4 mol. % of produced products from the reaction for at least about 5 hours. In certain embodiments, the Brunauer-Emmett-Teller (BET) surface area of the modified red mud catalyst composition is between about 50 m²/g and about 90 m²/g.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features, aspects, and advantages of the present disclosure will become better understood with regard to the following descriptions, claims, and accompanying drawings. It is to be noted, however, that the drawings illustrate only several embodiments of the disclosure and are therefore not to be considered limiting of the disclosure's scope as it can admit to other equally effective embodiments.

FIG. 1 is a graph showing conversion percentage for CH₄ in a bi-reforming process for unmodified red mud (RM) used as a catalyst and for acid nickel-molybdenum-modified red mud (ANMoMRM) used as a catalyst.

FIG. 2 is a graph showing mol. % of H₂ out of the total products produced from bi-reforming of CH₄ for unmodified red mud used as a catalyst and for ANMoMRM used as a catalyst.

DETAILED DESCRIPTION

So that the manner in which the features and advantages of the embodiments of compositions of Group VIB metal modified red mud, in some embodiments including nickel, along with systems and methods for bi-reforming with such compositions and for producing such compositions, may be understood in more detail, a more particular description of the embodiments of the present disclosure briefly summarized previously may be had by reference to the embodiments thereof, which are illustrated in the appended drawings, which form a part of this specification. It is to be noted, however, that the drawings illustrate only various embodiments of the disclosure and are therefore not to be considered limiting of the present disclosure's scope, as it may include other effective embodiments as well.

As noted, red mud is a caustic waste material generated during alumina extraction from bauxite ore. Red mud includes a mixture of transition metals, for example as listed in Table 1.

TABLE 1 Example composition ranges for global red mud. Component Fe₂O₃ Al₂O₃ SiO₂ Na₂O CaO TiO₂ Approx. 30-60% 10-20% 3-50% 2-10% 2-8% 10% Weight Percentage

Red mud was modified with nickel and molybdenum to be utilized and tested as a catalyst for bi-reforming as follows. In some embodiments, nickel is not required. In some embodiments, nickel in addition to or alternative to any one of or any combination of chromium, molybdenum, and tungsten can be used to modify red mud. Saudi Arabian red mud from Ma'aden Aluminium Company, based at Ras Al Khair, Saudi Arabia was used to prepare a modified catalyst composition. Table 2 shows the weight percent for certain components in the unmodified Saudi Arabian red mud composition.

TABLE 2 Certain component weight percentages in Saudi Arabian red mud (RM) catalyst/catalyst support composition. Component Fe₂O₃ Al₂O₃ SiO₂ Na₂O CaO TiO₂ Weight 18.75% 25.22% 18.88% 11.77% 7.97% 6.89% Percentage

The untreated red mud exhibited a Brunauer-Emmett-Teller (BET) surface area of about 16 m²/g.

Table 3 shows an example composition for one embodiment of produced nickel-molybdenum acid treated red mud for use as a modified catalyst. The unmodified red mud used as a catalyst precursor contained no detectable nickel or molybdenum.

TABLE 3 Example composition for a produced ANMoMRM used as a catalyst. Component Fe₂O₃ Al₂O₃ SiO₂ Na₂O CaO TiO₂ NiO MoO Weight 16.76% 21.43% 19.56% 2.81% 2.76% 5.36% 23.7% 5.06% Percentage

Because red mud is a highly variable waste material, elemental composition will vary between samples and test results.

Catalyst Preparation. An acid nickel-molybdenum-modified red mud (ANMoMRM) catalyst with 23.7 wt. % nickel oxide and 5.06 wt. % molybdenum oxide was prepared using a homogeneous precipitation process. Using an unmodified red mud catalyst precursor, 20 wt. % of nickel oxide (also referred to as NiO) was targeted to be loaded in the red mud to enhance bi-reforming activity, and 23.7 wt. % of nickel oxide was confirmed by X-ray fluorescence (XRF) analysis. Using the unmodified red mud catalyst precursor, 5 wt. % of molybdenum oxide (also referred to as MoO) was targeted to be loaded in the red mud to enhance bi-reforming activity, and 5.06 wt. % of molybdenum oxide was confirmed by XRF analysis. Depending on the catalyst application, nickel oxide can be loaded to a red mud precursor from between about 1 wt. % to about 50 wt. %, and molybdenum oxide, in addition to or alternative to other Group VIB metals, can be loaded to a red mud precursor from between about 1 wt. % to about 50 wt. %.

First, 10 g of Saudi Arabian red mud from Ma'aden Aluminium Company, based at Ras Al Khair, Saudi Arabia was modified by dissolving dried, unmodified red mud in 100 mL of deionized water, and then the pH was neutralized using 40.5 mL of 37 wt. % hydrochloric acid. Afterward, 10 g of nickel(II) nitrate hexahydrate was dissolved in 50 mL of ethanol. Then, 0.92 grams of ammonium molybdate tetrahydrate was dissolved in 50 mL of ethanol. The three separate solutions were mixed to form a mixed solution. Next the mixed solution was filtered solids were dried in an oven at 105° C., and then calcined at 600° C. for 4 hours. The final ANMoMRM solid product was ground to have a particle size of less than about 70 μm. The step of drying in an oven can last from about 2 to about 24 hours.

Other nickel-containing compounds and molybdenum-containing compounds can be used in addition to or alternative to nickel nitrate and ammonium molybdate, including any nickel-containing compounds or molybdenum-containing compounds soluble in ethanol or other organic or inorganic alcohols, or in aqueous ammonia. XRF in embodiments of the present disclosure confirmed the presence of nickel and molybdenum oxide loading in the ANMoMRM. Nickel can be combined with red mud to result in nickel(II) oxide, NiO, in addition to or alternative to nickel(III) oxide, Ni₂O₃. Molybdenum can be combined with red mud to result in (molybdenum dioxide, MoO₂) or Molybdenum(VI) oxide (molybdenum trioxide, MoO₃).

BET surface area analysis showed unmodified red mud surface area was about 16 m²/g. BET surface area for acid modified red mud was about 170 m²/g. BET surface area for acid modified red mud with nickel in addition to or alternative to molybdenum loading is, in some embodiments, between about 50 m²/g and about 90 m²/g, for example about 63 m²/g or about 89 m²/g.

Catalyst testing. Several tests on red mud catalytic activity and ANMoMRM catalytic activity for bi-reforming were experimentally conducted. Red mud was tested as received without any modifications, and it was placed in a Micromeritics® PID Eng & Tech brand microactivity reactor designed for catalyst activity and selectivity analysis, and the same was done for the prepared ANMoMRM catalyst. The results are compared, for example, in FIGS. 1 and 2. Results show that ANMoMRM catalytic activity for bi-reforming is advantageously improved over non-modified red mud catalytic activity for bi-reforming.

FIG. 1 is a graph showing conversion percentage for CH₄ in a bi-reforming process for unmodified red mud (RM) used as a catalyst and for ANMoMRM used as a catalyst. Effects of nickel addition to red mud were studied. Experimental conditions in the bi-reforming reactor included temperature at about 750° C., pressure at about 14 bar, and gas hourly space velocity (GHSV) at about 7362 h⁻¹. The test was conducted for 6 hours. The feed was 50 mol. % methane, 17 mol. % CO₂, and 33 mol. % steam for both catalysts tested. The GHSV was calculated for the mixed feed. GHSV generally measures the flow rate of the feed gases divided by the catalyst volume, which indicates the residence time of the reactants on the catalyst. For bi-reforming, the feed composition can comprise, consist essentially of, or consist of CH₄, CO₂, and steam. Based in part on thermodynamics, a suitable molar ratio of methane:carbon dioxide:steam is about 3:1:2.

Methane conversion illustrated in FIG. 1 shows ANMoMRM catalyst outperformed its counterpart, the untreated red mud. Methane conversion by ANMoMRM reached up to about 35%, then stabilized at about 5%. On the other hand unmodified red mud was not effective as a catalyst for conversion of methane. The greater conversion rate of ANMoMRM can be attributed to the addition of nickel and molybdenum, and synergies of the nickel and molybdenum with the existing transition metals in the red mud.

FIG. 2 is a graph showing mol. % of H₂ out of the total products produced from bi-reforming of CH₄ for unmodified red mud used as a catalyst and for ANMoMRM used as a catalyst. Hydrogen production illustrated in FIG. 2 shows that untreated red mud produced low amounts of hydrogen, whereas ANMoMRM catalyst produced between about 4 mol. % and about 7 mol. % hydrogen. Nickel-molybdenum modification of red mud has enhanced the performance significantly.

The singular forms “a,” “an,” and “the” include plural referents, unless the context clearly dictates otherwise. The term “about” when used with respect to a value or range refers to values including plus and minus 5% of the given value or range.

In the drawings and specification, there have been disclosed example embodiments of the present disclosure, and although specific terms are employed, the terms are used in a descriptive sense only and not for purposes of limitation. The embodiments of the present disclosure have been described in considerable detail with specific reference to these illustrated embodiments. It will be apparent, however, that various modifications and changes can be made within the spirit and scope of the disclosure as described in the foregoing specification, and such modifications and changes are to be considered equivalents and part of this disclosure. 

What is claimed is:
 1. A method for bi-reforming over an enhanced-acidity modified red mud catalyst composition, the method comprising the steps of: providing a methane feed in the presence of carbon dioxide and steam to react in a bi-reforming reaction over the enhanced-acidity modified red mud catalyst composition at a temperature between about 500° C. to about 1000° C. and a pressure between about 5 bar and 20 bar to produce synthesis gas comprising H₂ and CO, the enhanced-acidity modified red mud catalyst composition prepared by a homogeneous precipitation process comprising the steps of: providing an unmodified caustic red mud waste material produced from an alumina extraction process from bauxite ore; dissolving in water the unmodified caustic red mud waste material and neutralizing pH of the unmodified red mud waste material with an acid comprising hydrochloric acid; combining nickel oxide, the nickel oxide present at between about 5 wt. % to about 40 wt. % of the enhanced-acidity modified red mud catalyst composition; and combining a Periodic Table Group VIB metal oxide, the Group VIB metal oxide present at between about 1 wt. % and about 30 wt. % of the enhanced-acidity modified red mud catalyst composition.
 2. The method according to claim 1, where the Group VIB metal oxide comprises at least one metal selected from the group consisting of: chromium, molybdenum, and tungsten.
 3. (canceled)
 4. The method according to claim 1, where the increased temperature is between about 600° C. to about 800° C.
 5. The method according to claim 1, where the increased temperature is about 750° C.
 6. (canceled)
 7. The method according to claim 1, where the increased pressure is between about 10 bar and about 15 bar.
 8. The method according to claim 1, where the increased pressure is about 14 bar.
 9. The method according to claim 1, where gas hourly space velocity of the methane feed in the presence of carbon dioxide and steam is between about 1000 h⁻¹ to 10000 h⁻¹.
 10. The method according to claim 1, where the enhanced-acidity modified red mud catalyst composition includes at least one component selected from the group consisting of Fe₂O₃, Al₂O₃, SiO₂, Na₂O, CaO, and TiO₂.
 11. The method according to claim 1, where a majority of particles of the enhanced-acidity modified red mud catalyst composition have a particle size of less than about 70 μm.
 12. The method according to claim 1, where the nickel oxide is present at between about 10 wt. % to about 30 wt. % of the enhanced-acidity modified red mud catalyst composition.
 13. The method according to claim 1, where the nickel oxide is present at between about 15 wt. % to about 25 wt. % of the enhanced-acidity modified red mud catalyst composition.
 14. The method according to claim 1, where the nickel oxide is present at about 23 wt. % of the enhanced-acidity modified red mud catalyst composition.
 15. The method according to claim 1, where the Group VIB metal oxide is present at between about 1 wt. % to about 20 wt. % of the enhanced-acidity modified red mud catalyst composition.
 16. The method according to claim 1, where the Group VIB metal oxide is present at between about 1 wt. % to about 10 wt. % of the enhanced-acidity modified red mud catalyst composition.
 17. The method according to claim 1, where the Group VIB metal oxide is present at about 5 wt. % of the enhanced-acidity modified red mud catalyst composition.
 18. The method according to claim 1, where conversion percentage of methane reaches up to about 35%.
 19. The method according to claim 1, where a molar ratio of methane:carbon dioxide:steam is about 3:1:2.
 20. The method according to claim 1, where produced H₂ from the bi-reforming reaction is at least about 4 mol. % of produced products from the bi-reforming reaction for at least about 5 hours.
 21. The method according to claim 1, where the Brunauer-Emmett-Teller (BET) surface area of the modified red mud catalyst composition is between about 50 m²/g and about 90 m²/g. 